CN101121806A - ABS color master batch with increased color stability and preparation method thereof - Google Patents
ABS color master batch with increased color stability and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to the plastics coloring field and discloses an ABS color master batch with the improved color stability and the preparation method. The ABS master batch of the present invention consists of the following components and weight percentages: 20 to 99 percent of carrier, 0.01 to 70 percent of toner powder, 0 to 40 percent of dispersant, 0.1 to 2 percent of thermal stabilizer, 0 to 10 percent of processing aid, and 0 to 70 percent of filler. The carrier is one of or the mixture of a plurality of the acrylonitrile-styrene copolymer (AS), the ethylene-acetate (EVA), the ethylene-acrylic, the vinyl-crylic ester, and the ethylene-methyl crylic ester. The ABS color master batch provided by the present invention has the advantages of the improved color stability and the smaller color difference while coloring the ABS product; the present invention overcomes the problems in the existing ABS color master batch of the color instability and the larger color difference; the ABS color master batch of the present invention can replace the ABS pull particle to color so as to save the energy and reduce the production cost; the application prospects are broad.
Description
Technical field
The present invention relates to field of plastic coloring, specifically, relate to ABS Masterbatch of a kind of colour stability raising and preparation method thereof.
Background technology
ABS resin is vinyl cyanide, divinyl and cinnamic terpolymer, can adopt blending method, copolymerization method and emulsion graft polymerization method to produce.Have the ultrahigh impact type by regulating three kinds of monomeric compositions among the ABS, can preparing, the material of the universal and special type various trades mark such as (as electroplating level).Adopt the plastics of ABS material preparation nontoxic, tasteless, rigidity and tough performance satisfy the requirement in fields such as household electrical appliance, light industry stationery sports goods, automotive industry and chemical industry, and its application is very extensive.
At present, the household electrical appliance plastic fittings of many higher gears mainly adopts ABS plastic.Personalized and the differential development trend along with tame electrical article, the color of household electrical appliance develops towards the direction of diversification and bright-colouredization, and painted requirement is also being improved day by day.There is some difference with forming the ABS color and luster that causes the various trades mark for the molecular structure of ABS terpolymer, and this is painted totally unfavorable for goods.Therefore, the ABS plastic product of the man electrical article of many top grades can't solve the problem of flow liner and colour stability when adopting Masterbatch painted, usually have to adopt and draw grain painted.It is to adopt mixing facilities such as twin screw extruder to carry out melt blending ABS and toner mixing back that employing draws grain painted, thereby makes painted ABS micelle.With adopt that Masterbatch is painted to be compared, ABS need experience thermal history twice, has damaged the mechanical property of goods to a certain extent.Because it is painted to draw grain whole ABS materials need be carried out granulation when painted, energy consumption is big, production cost is high, storage and traffic capacity are very big.Under the situation that current energy shortage, material price soar, adopt the painted advantage of Masterbatch very obvious, can not only save energy, and can reduce painted cost.
Parts such as white domestic appliances such as air-conditioning, refrigerator and washing machine adopt Masterbatch to carry out when painted, because it is carrier that common Masterbatch generally adopts ABS, adding proportion less (being generally 4phr), exist the flowing property of Masterbatch relatively poor, add content that the color of white domestic appliances requires titanium dioxide in the Masterbatch up to 40～60%, Masterbatch proportion is big, and (what have surpasses 2.0g/cm
3), Masterbatch sinks to the bottom easily and causes Masterbatch macroscopical skewness in plastics when forming process, occurs problems such as color instability, aberration be wayward easily.Along with the client to improving constantly that product appearance requires, ABS plastic processing enterprise has higher requirement to the stability of color,
Summary of the invention
The objective of the invention is at present ABS Masterbatch have the not good problem of colour stability, the ABS Masterbatch that provides a kind of colour stability obviously to be improved when painted.
Another object of the present invention provides the preparation method of above-mentioned ABS Masterbatch.To achieve these goals, ABS Masterbatch of the present invention is made up of following component and weight percentage: carrier 20～99%, toner 0.01～70%, dispersion agent 0～40%, thermo-stabilizer 0.1～2%, processing aid 0～10%, filler 0～70%; Described carrier is one or more mixtures in acrylonitritrile-styrene resin (AS), ethane-acetic acid ethyenyl ester (EVA), ethylene-propylene acids, ethylene-acrylate class, the ethylene-methyl acrylate class; The preparation method of carrier is: at normal temperatures and pressures, component was mixed in high-speed mixer 1～5 minute, adopt twin screw extruder to carry out melt blending, temperature is controlled to be 120～220 ℃, screw speed is 200r/min, even by the shearing of screw rod, the mixing material mixing that makes, carry out granulation then, drying makes carrier.
Above-mentioned ethylene-propylene acids is ethylene-acrylic acid copolymer (EAA); Above-mentioned ethylene-acrylate class is ethylene-acrylate copolymer (EBA); Above-mentioned ethylene-methyl acrylate class is ethylene-methyl acrylate multipolymer (EMA); Adopt this carrier to have the following advantages: the one, the AS flowing property better and compatible with ABS better, the 2nd, EVA, EAA, EMA etc. with not only have certain consistency with ABS, and very favourable to dispersing of pigments.
Above-mentioned toner can be one or more the mixture in mineral dye, pigment dyestuff or the dyestuff.Described mineral dye is titanium dioxide (titanium dioxide), carbon black or zinc sulfide white etc.; Described pigment dyestuff is azo pigment, heterocycle pigment or miscellany pigment etc.; Described dyestuff is anthraquinone, piceneketone and derivative thereof etc.
Above-mentioned dispersion agent is one or more the mixture in polyethylene wax, oxidized polyethlene wax, ethylene-vinyl acetate copolymer wax (EVA wax), ionic polymer wax (as the AC-295A of HONEYWEILL), the polyamide wax (EBS, modification EBS etc.).The preferential fusion and be coated on the granules of pigments surface in the course of processing of these low-molecular-weight components, thus play the effect that promotes dispersing of pigments and make it stabilization.
Above-mentioned thermo-stabilizer is phenolic antioxidant or phosphite antioxidant or its mixture.Phenolic antioxidant, as four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), 2,6-two (1-phenyl) ethyl-4-nonylphenol (1076), 2,6 di tert butyl 4 methyl phenol (264, BHT); Phosphite ester kind antioxidant is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (168), four (2,4-di-tert-butyl-phenyl-4,4 '-xenyl) bis-phosphite (PEPQ), three (nonyl phenyl) phosphorous acid ester (TNPP), distearyl pentaerythritol diphosphite (PEP8) or tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester (626) etc.The adding of thermo-stabilizer can avoid in the Masterbatch course of processing vector resin to degrade, and reaches the effect that keeps the Masterbatch colour stable.
Above-mentioned processing aid is one or more the mixture in stearic acid, stearate, white mineral oil, phthalic ester plasticizer, citric acid ester plasticizer or the silicone.The adding of processing aid can reduce the frictional force of material and machine barrel, die surface, has solved problems such as surface gloss is not good, demoulding difficulty.
Above-mentioned filler is one or more the mixture in lime carbonate, talcum powder, barium sulfate or the wollastonite.
The preparation method of above-mentioned ABS Masterbatch is: each component is prepared burden in proportion, in high-speed mixer, mixed then 5～20 minutes, adopt twin screw extruder to carry out melt blending, temperature is controlled at 110～200 ℃, screw speed is 50～400r/min, be uniformly dispersed in vector resin by the shearing of screw rod or rotor, the mixing pigment that makes, carry out granulation then, drying makes Masterbatch of the present invention.
The present invention also can adopt the Banbury mixer banburying earlier with the material that mixes in the high-speed mixer, adopts the operational path of single screw extrusion machine granulation to prepare Masterbatch of the present invention then.
Compared with prior art, the present invention has following beneficial effect: when ABS Masterbatch provided by the invention is applied to ABS goods painted, have colour stability raising, the less advantage of aberration, problems such as existing ABS Masterbatch color instability when painted, aberration be bigger have been overcome, can replace ABS draws grain painted, save energy and reducing production costs has a extensive future.
Embodiment
Embodiment 1
At normal temperatures and pressures, AS with 80% mixed in high-speed mixer 2 minutes with 20% EVA, adopt twin screw extruder to carry out melt blending, temperature is controlled to be 120 ℃, screw speed is 20r/min, shearing by screw rod, mixingly make two kinds of material mixing even, carry out granulation then, drying makes required Masterbatch carrier A 1 of the present invention.
At normal temperatures and pressures, with following component and weight percentage: carrier A 155%, titanium dioxide 40%, polyethylene wax 8%, phenolic antioxidant BHT2%, stearic acid 1%, lime carbonate 4%, carried out high-speed mixing 10 minutes in high-speed mixer, and adopted twin screw extruder to carry out melt blending, temperature is controlled at 200 ℃, screw speed is 200r/min, be uniformly dispersed in vector resin by the shearing of screw rod, the mixing pigment that makes, carry out tie rod pelletizing (the Masterbatch outward appearance is cylindric), drying, packing then, make Masterbatch B1 of the present invention.
Embodiment 2
At normal temperatures and pressures, AS with 70% mixed in high-speed mixer 5 minutes with 30% EMA, adopt twin screw extruder to carry out melt blending, temperature is controlled to be 220 ℃, screw speed is 200r/min, shearing by screw rod, mixingly make two kinds of material mixing even, carry out granulation then, drying makes required Masterbatch carrier A 2 of the present invention.
At normal temperatures and pressures, with following component and weight percentage: carrier A 235%, titanium dioxide 30%, EBS 10%, phosphorous acid ester 168 1%, silicone 2%, wollastonite 22%, carried out high-speed mixing 15 minutes in high-speed mixer, and adopted twin screw extruder to carry out melt blending, temperature is controlled at 200 ℃, screw speed is 100r/min, be uniformly dispersed in vector resin by the shearing of screw rod, the mixing pigment that makes, carry out tie rod pelletizing (the Masterbatch outward appearance is cylindric), drying, packing then, make Masterbatch of the present invention.
Embodiment 3
At normal temperatures and pressures, AS with 50% mixed in high-speed mixer 3 minutes with 50% EAA, adopt twin screw extruder to carry out melt blending, temperature is controlled to be 160 ℃, screw speed is 200r/min, shearing by screw rod, mixingly make two kinds of material mixing even, carry out granulation then, drying makes required Masterbatch carrier A 3 of the present invention.
At normal temperatures and pressures, with following component and weight percentage: carrier A 330%, titanium dioxide 15%, zinc sulfide white 5%, azo pigment 0.5%, oxidized polyethlene wax 1%, ethene-vinyl acetate wax 1.5%, phenolic antioxidant 1,076 1%, phosphorous acid ester 1680.5%, stearic acid 2%, stearate 2%, white mineral oil 2%, silicone 2%, lime carbonate 3%, talcum powder 5%, wollastonite 2.5%, in high-speed mixer, mix, adopt the Banbury mixer banburying earlier, adopt screw extrusion press to carry out tie rod pelletizing (the Masterbatch outward appearance is cylindric) then, make Masterbatch of the present invention.
In order to contrast the advantage of the present invention and prior art, compare test according to Comparative Examples 1～3 prescription, the preparation method of Comparative Examples 1～3 preparation method with embodiment 1～3 respectively is identical.
Comparative Examples 1
ABS40%, titanium dioxide 40%, EVA wax 5%, EBS3%, thermo-stabilizer 10100.4%, thermo-stabilizer 168 0.6%, Zinic stearas 0.5%, lime carbonate 10.5%.
Comparative Examples 2
ABS 40%, titanium dioxide 30%, and carbon black 0.1%, EVA wax 4%, EBS 2%, thermo-stabilizer 1,010 0.4%, thermo-stabilizer 168 0.6%, Zinic stearas 0.5%, talcum powder 22.4%.
Comparative Examples 3
ABS 40%, titanium dioxide 15%, and phthalocyanine blue 1%, EVA wax 3%, EBS 3%, thermo-stabilizer 1,010 0.4%, thermo-stabilizer 168 0.6%, Zinic stearas 0.5%, lime carbonate 20%, talcum powder 16.5%.
Masterbatch with embodiment and comparative example preparation adds 4phr injection moulding colour table in ABS plastic, concrete comparing result is as shown in table 1.
Table 1 adopts the evaluation of different carriers coloring effect
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| The flow liner aberration | Do not have≤0.4 | Do not have≤0.5 | Do not have≤0.5 | Seriously≤1.1 | Have≤0.9 | A little≤0.8 |
From as can be known above-mentioned, adopt ABS Masterbatch of the present invention to be used for the ABS color articles, more painted than existing ABS Masterbatch is that aberration obviously reduces, colour stability is significantly improved.
Embodiment 4～6
The prescription of embodiment 4,5,6 is identical with embodiment 1,2,3 respectively, and its difference is pelletizing technology difference, promptly adopts die face cutting, Masterbatch outward appearance rounded laminar (similar tablet).In ABS plastic, add 4phr injection moulding colour table, measure aberration.
Comparative Examples 4～6
The prescription of Comparative Examples 4,5,6 is identical with Comparative Examples 1,2,3 respectively, and its difference is pelletizing technology difference, promptly adopts die face cutting, Masterbatch outward appearance rounded laminar (similar tablet).Add 4phr injection moulding colour table in ABS plastic, measure aberration, concrete comparing result is as shown in table 2.
Table 2 adopts the evaluation of different pellet cutting method coloring effects
| Sample | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 |
| The flow liner aberration | Do not have≤0.3 | Do not have≤0.4 | Do not have≤0.4 | Have≤0.9 | On a small quantity≤0.7 | A little≤0.5 |
Contrast table 1, table 2 result as can be known, comparative example and embodiment adopt and are laminar pelletizing technology and further reduce than cylindric painted aberration, account for color stability is better.When its reason is to adopt laminar pelletizing technology, the number of 1g Masterbatch is than adopting cylindric pelletizing technology to Duo 20～30%, the number of colored spots increases more, and laminar Masterbatch is not easy to sink to the bottom in the process of batch mixing relatively, and the macroscopic view of Masterbatch in plastics distributes more even; In molding process, laminar Masterbatch heating surface area is bigger than columned, the fusion plastification better effects if, and its final result is that aberration diminishes, colour stability obviously improves.
Comparative Examples 7
For Masterbatch coloring effect of the present invention relatively, adopt and draw that grain is painted to access identical color, the injection moulding model is also measured aberration, with the Masterbatch coloring effect relatively see Table 3.
Table 3 Masterbatch is painted to be compared with drawing a coloring effect
| Sample | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 7 |
| The flow liner aberration | Do not have≤0.3 | Do not have≤0.4 | Do not have≤0.4 | Thing≤0.3 |
More as can be known, adopt the coloring effect of the painted ABS plastic of Masterbatch of the present invention to reach and draw the painted level of grain from table 3, can replace fully and draw grain painted.
Draw that grain painted and Masterbatch are painted to see Table 4 and table 5 in energy consumption and the difference that is coloured to this aspect.
Table 4 Masterbatch compares with drawing the painted energy consumption of grain
| The contrast project | Masterbatch is painted | Draw grain painted |
| Industry average power consumption (kilowatt-hour/ton) | 250 | 300 |
| The painted amount of finish of ABS per ton (ton) | 0.04 | 1 |
| The painted current consumption of ABS per ton (kilowatt-hour) | 10 | 300 |
Table 5 Masterbatch compares with drawing the painted cost of grain
| The contrast project | Masterbatch is painted | Draw grain painted |
| ABS tinting material addition per ton | 40(Kg) | |
| The tinting material average unit cost | 25 (unit/Kg | |
| ABS per ton consumes tinting material price (unit/ton) | 1000 | |
| The resin valency * (unit/ton) of deduction tinting material weight | -620 | |
| The painted real cost of ABS resin per ton (unit/ton) | 380 | 2000 |
* remarks: by 15.5 yuan/Kg of present ABS market unit price.
More as can be known, adopting and drawing the painted energy consumption of grain is painted 30 times of Masterbatch, and the painted save energy greatly of Masterbatch is described from table 4.As known from Table 5, adopt draw the painted cost of grain be Masterbatch painted more than five times, adopt 1620 yuan of the painted about costs per ton of Masterbatch, its economic benefit is obvious.
From as can be known above-mentioned, ABS Masterbatch coloring effect of the present invention is significantly improved than existing Masterbatch product, has reached the level of drawing grain painted, and energy consumption and painted cost reduce greatly, have tangible technical superiority, and can produce good economic and social benefit.
Claims (10)
1. an ABS Masterbatch is characterized in that being made up of following component and weight percentage: carrier 20～99%, toner 0.01～70%, dispersion agent 0～40%, thermo-stabilizer 0.1～2%, processing aid 0～10%, filler 0～70%; Described carrier is one or more the mixture in acrylonitritrile-styrene resin, ethane-acetic acid ethyenyl ester, ethylene-propylene acids, ethylene-acrylate class, the ethylene-methyl acrylate class.
2. ABS Masterbatch as claimed in claim 1 is characterized in that described ethylene-propylene acids is an ethylene-acrylic acid copolymer; Described ethylene-acrylate class is an ethylene-acrylate copolymer; Described ethylene-methyl acrylate class is the ethylene-methyl acrylate multipolymer; The preparation method of described carrier is: at normal temperatures and pressures, component was mixed in high-speed mixer 1～5 minute, adopt twin screw extruder to carry out melt blending, temperature is controlled to be 100～220 ℃, screw speed is 50～400r/min, even by the shearing of screw rod, the mixing material mixing that makes, carry out granulation then, drying makes carrier.
3. ABS Masterbatch as claimed in claim 1 is characterized in that described toner is one or more the mixture in mineral dye, pigment dyestuff or the dyestuff.
4. ABS Masterbatch as claimed in claim 1 is characterized in that described dispersion agent is one or more the mixture in polyethylene wax, oxidized polyethlene wax, ethylene-vinyl acetate copolymer wax, ionic polymer wax, the polyamide wax.
5. ABS Masterbatch as claimed in claim 1 is characterized in that described thermo-stabilizer is phenolic antioxidant or phosphite antioxidant or its mixture.
6. ABS Masterbatch as claimed in claim 5, it is characterized in that described phenolic antioxidant is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,6-two (1-phenyl) ethyl-4-nonylphenol, 2,6 di tert butyl 4 methyl phenol; Described phosphite ester kind antioxidant is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, four (2,4-di-tert-butyl-phenyl-4,4 '-xenyl) bis-phosphite, three (nonyl phenyl) phosphorous acid ester, distearyl pentaerythritol diphosphite or tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
7. ABS Masterbatch as claimed in claim 1 is characterized in that described processing aid is one or more the mixture in stearic acid, stearate, white mineral oil, phthalic ester plasticizer, citric acid ester plasticizer or the silicone.
8. ABS Masterbatch as claimed in claim 1 is characterized in that described filler is one or more the mixture in lime carbonate, talcum powder, barium sulfate or the wollastonite.
9. the preparation method of the described ABS Masterbatch of claim 1, it is characterized in that comprising the steps: each component is prepared burden in proportion, in high-speed mixer, mixed then 5～20 minutes, adopt twin screw extruder to carry out melt blending, temperature is controlled at 100～220 ℃, screw speed is 50～400r/min, is uniformly dispersed in carrier by the shearing of screw rod or rotor, the mixing pigment that makes, and carries out granulation then, drying makes the ABS Masterbatch.
10. the preparation method of the described ABS Masterbatch of claim 1, it is characterized in that comprising the steps: each component is prepared burden in proportion, in high-speed mixer, mix then, adopt the twin screw extruder melting mixing, and adopt tie rod pelletizing or die face cutting to make the ABS Masterbatch; Also can adopt the Banbury mixer banburying earlier, adopt single screw extrusion machine to carry out tie rod pelletizing or die face cutting then, make the ABS Masterbatch.
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